JP2021133363A - Atomizer for forming film and film formation apparatus using the same - Google Patents

Atomizer for forming film and film formation apparatus using the same Download PDF

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JP2021133363A
JP2021133363A JP2021016942A JP2021016942A JP2021133363A JP 2021133363 A JP2021133363 A JP 2021133363A JP 2021016942 A JP2021016942 A JP 2021016942A JP 2021016942 A JP2021016942 A JP 2021016942A JP 2021133363 A JP2021133363 A JP 2021133363A
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raw material
film
ultrasonic
film forming
generation source
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JP6975417B2 (en
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洋 橋上
Hiroshi Hashigami
洋 橋上
敏幸 川原村
Toshiyuki Kawaramura
敏幸 川原村
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Shin Etsu Chemical Co Ltd
Kochi Prefectural University Corp
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Kochi Prefectural University Corp
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    • CCHEMISTRY; METALLURGY
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    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/448Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
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    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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    • C23C16/30Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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Abstract

To provide an atomizer for forming film capable of forming a high-quality thin film in which particle adhesion is suppressed.SOLUTION: An atomizer for forming film has a raw material container for storing a raw material solution, a cylindrical member that spatially connects the inside and outside of the raw material container and is installed so that a lower end thereof does not come into contact with a liquid surface of the raw material solution in the raw material container, an ultrasonic generator having one or more ultrasonic generation sources that emit ultrasonic waves, and a liquid tank that propagates the ultrasonic waves to the raw material solution via an intermediate liquid. The ultrasonic generation source is located outside the liquid tank. The center of the ultrasonic generation source is located between a surface formed by an inner extension of a side wall of the raw material container and a surface formed by an outer extension of a side wall of the cylindrical member. When a center line of an ultrasonic emission surface of the ultrasonic generation source is u, the ultrasonic generation source is provided so that the center line u does not intersect with the side wall of the cylindrical member.SELECTED DRAWING: Figure 1

Description

本発明は、成膜用霧化装置およびこれを用いた成膜装置に関する。 The present invention relates to a film forming atomizer and a film forming apparatus using the same.

霧化されたミスト状の原料を用いて、基板上に薄膜を形成させるミスト化学気相成長法(Mist Chemical Vapor Deposition:Mist CVD。以下、「ミストCVD法」ともいう)が開発され、酸化物半導体膜などの作製に用いられている(特許文献1、2)。ミストCVD法での膜形成では超音波によりミストを得る方式が一般的である。 A mist chemical vapor deposition (Mist CVD, hereinafter also referred to as "mist CVD method") in which a thin film is formed on a substrate using an atomized mist-like raw material has been developed, and oxides have been developed. It is used for manufacturing semiconductor films and the like (Patent Documents 1 and 2). In film formation by the mist CVD method, a method of obtaining mist by ultrasonic waves is common.

特開2013−028480号公報Japanese Unexamined Patent Publication No. 2013-028480 特開2014−063973号公報Japanese Unexamined Patent Publication No. 2014-063973

しかしながら、これまで高品質な膜を形成するための原料霧化手法は確立されておらず、原料ミストの品質に起因したパーティクルが、作製した膜に多数付着する問題があった。また、成膜速度を高める場合などにミスト供給量を増加させると、このようなパーティクル付着がより顕著になることが知られており、膜品質と生産性の両立が課題であった。 However, a raw material atomization method for forming a high-quality film has not been established so far, and there is a problem that a large number of particles due to the quality of the raw material mist adhere to the produced film. Further, it is known that such particle adhesion becomes more remarkable when the amount of mist supplied is increased, such as when the film forming speed is increased, and it has been an issue to achieve both film quality and productivity.

本発明は、上記問題を解決するためになされたものであり、パーティクル付着が抑制された高品質な薄膜を効率良く形成可能とする成膜用霧化装置、およびこれを用いて高品質な膜を高い生産性で形成するための成膜装置を提供することを目的とする。 The present invention has been made to solve the above problems, and is an atomizing device for film formation capable of efficiently forming a high-quality thin film in which particle adhesion is suppressed, and a high-quality film using the atomizing device for film formation. It is an object of the present invention to provide a film forming apparatus for forming a film with high productivity.

本発明は、上記目的を達成するためになされたものであり、原料溶液を収容する原料容器と、前記原料容器の内部と外部を空間的に接続し、且つその下端が前記原料容器内において前記原料溶液の液面に触れないように設置された筒状部材と、超音波を照射する超音波発生源を一つ以上有する超音波発生器と、前記超音波を前記原料溶液に中間液を介して伝播させる液槽とを有する成膜用霧化装置であって、前記超音波発生源は、前記液槽の外側にあり、前記超音波発生源の中心が前記原料容器の側壁の内側の延長がなす面と前記筒状部材の側壁の外側の延長がなす面との間にあり、前記超音波発生源の超音波射出面の中心線をuとしたとき、前記中心線uが前記筒状部材の側壁と交わらないように超音波発生源が設けられている成膜用霧化装置を提供する。 The present invention has been made to achieve the above object, and the raw material container for accommodating the raw material solution and the inside and the outside of the raw material container are spatially connected, and the lower end thereof is described in the raw material container. A tubular member installed so as not to touch the liquid surface of the raw material solution, an ultrasonic generator having one or more ultrasonic wave generation sources for irradiating ultrasonic waves, and the ultrasonic waves being passed through an intermediate solution to the raw material solution. An atomizer for film formation having a liquid tank for propagating the sound wave, the ultrasonic wave generation source is outside the liquid tank, and the center of the ultrasonic wave generation source is an extension inside the side wall of the raw material container. The center line u is the tubular shape when the center line of the ultrasonic wave emitting surface of the ultrasonic wave generation source is u, which is between the surface formed by the surface and the surface formed by the outer extension of the side wall of the tubular member. Provided is a film forming atomizer provided with an ultrasonic wave generation source so as not to intersect the side wall of the member.

このような成膜用霧化装置であれば、成膜に適した、高品質で良好な高密度ミストを安定して得ることができるものとなるため、パーティクルの少ない高品質な膜を効率良く形成可能な成膜用霧化装置となる。 With such a film-forming atomizer, it is possible to stably obtain high-quality and good high-density mist suitable for film formation, so that a high-quality film with few particles can be efficiently obtained. It is a film-forming atomizer that can be formed.

このとき、前記超音波発生源の中心を通り、前記筒状部材の外壁と平行な直線と前記筒状部材の外壁との距離dが、5mm以上となるように超音波発生源が設けられていることが好ましい。 At this time, the ultrasonic wave generation source is provided so that the distance d between the straight line passing through the center of the ultrasonic wave generation source and parallel to the outer wall of the tubular member and the outer wall of the tubular member is 5 mm or more. It is preferable to have.

このようにすれば、より高密度のミストをより安定して得ることができるものとなる。 In this way, a higher density mist can be obtained more stably.

また、原料溶液を霧化して原料ミストを形成する霧化手段と、前記ミストを基体に供給して前記基体上に膜を形成する成膜手段とを少なくとも具備する成膜装置であって、前記霧化手段として上記の成膜用霧化装置を具備する成膜装置を提供する。 A film forming apparatus comprising at least an atomizing means for atomizing a raw material solution to form a raw material mist and a film forming means for supplying the mist to a substrate to form a film on the substrate. As an atomizing means, a film forming apparatus including the above-mentioned film forming atomizing apparatus is provided.

このような装置とすれば、高品質な膜を高い生産性で製造することができるものとなる。 With such an apparatus, a high-quality film can be produced with high productivity.

以上のように、本発明によれば、高品質で高密度なミストが安定して得られる成膜用霧化装置を提供できる。また、本発明によれば、高い生産性で高品質な膜を製造可能な成膜装置を提供できる。 As described above, according to the present invention, it is possible to provide an atomizing apparatus for film formation, which can stably obtain high-quality and high-density mist. Further, according to the present invention, it is possible to provide a film forming apparatus capable of producing a high-quality film with high productivity.

本発明に係る成膜用霧化装置の構成を示した図である。It is a figure which showed the structure of the atomization apparatus for film formation which concerns on this invention. 本発明に係る成膜用霧化装置のミスト発生部を説明する図である。It is a figure explaining the mist generation part of the atomization apparatus for film formation which concerns on this invention. 本発明に係る成膜装置の構成の一形態を説明する図である。It is a figure explaining one form of the structure of the film forming apparatus which concerns on this invention. 本発明に係る成膜装置の構成の別の形態を説明する図である。It is a figure explaining another form of the structure of the film forming apparatus which concerns on this invention.

以下、本発明を詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

上述のように、パーティクル付着が抑制された高品質な薄膜を形成可能とする成膜用霧化装置、およびこれを用いて高品質な膜を高い生産性で形成するための成膜装置が求められていた。 As described above, there is a need for a film-forming atomizer capable of forming a high-quality thin film in which particle adhesion is suppressed, and a film-forming device for forming a high-quality film using the atomizing device with high productivity. Was being done.

本発明者らは、上記課題について鋭意検討を重ねた結果、原料溶液を収容する原料容器と、前記原料容器の内部と外部を空間的に接続し、且つその下端が前記原料容器内において前記原料溶液の液面に触れないように設置された筒状部材と、超音波を照射する超音波発生源を一つ以上有する超音波発生器と、前記超音波を前記原料溶液に中間液を介して伝播させる液槽とを有する成膜用霧化装置であって、前記超音波発生源は、前記液槽の外側にあり、前記超音波発生源の中心が前記原料容器の側壁の内側の延長がなす面と前記筒状部材の側壁の外側の延長がなす面との間にあり、前記超音波発生源の超音波射出面の中心線をuとしたとき、前記中心線uが前記筒状部材の側壁と交わらないように超音波発生源が設けられている成膜用霧化装置により、パーティクル付着が抑制された高品質な薄膜を高い生産性で形成できるものとなることを見出し、本発明を完成した。 As a result of diligent studies on the above problems, the present inventors spatially connect the raw material container containing the raw material solution and the inside and the outside of the raw material container, and the lower end thereof is the raw material in the raw material container. A tubular member installed so as not to touch the liquid surface of the solution, an ultrasonic generator having one or more ultrasonic generation sources for irradiating ultrasonic waves, and the ultrasonic waves being passed through an intermediate solution to the raw material solution. An atomizer for film formation having a liquid tank for propagating, the ultrasonic source is on the outside of the liquid tank, and the center of the ultrasonic source is an extension of the inside of the side wall of the raw material container. It is located between the forming surface and the surface formed by the outer extension of the side wall of the tubular member, and when the center line of the ultrasonic emitting surface of the ultrasonic source is u, the center line u is the tubular member. We have found that a high-quality thin film in which particle adhesion is suppressed can be formed with high productivity by an ultrasonic atomizing device provided with an ultrasonic source so as not to intersect with the side wall of the present invention. Was completed.

以下、図面を参照して説明する。 Hereinafter, description will be made with reference to the drawings.

(成膜用霧化装置)
図1に、本発明に係る成膜用霧化装置100を示す。成膜用霧化装置100は、原料溶液114を収容する原料容器111と、原料容器111の内部と外部を空間的に接続し、且つその下端が原料容器111内において原料溶液114の液面に触れないように設置された筒状部材113と、超音波を照射する超音波発生源(超音波振動板)121を一つ以上有する超音波発生器120と、超音波を原料溶液114に中間液123を介して伝播させる液槽122とを具備する。
(Atomizer for film formation)
FIG. 1 shows a film forming atomizer 100 according to the present invention. The film forming atomizer 100 spatially connects the raw material container 111 containing the raw material solution 114 and the inside and the outside of the raw material container 111, and the lower end thereof is on the liquid surface of the raw material solution 114 in the raw material container 111. A tubular member 113 installed so as not to touch, an ultrasonic generator 120 having one or more ultrasonic generation sources (ultrasonic vibrating plates) 121 for irradiating ultrasonic waves, and an intermediate liquid in which ultrasonic waves are mixed with a raw material solution 114. It includes a liquid tank 122 that propagates through 123.

原料容器111にはキャリアガス131を導入するためのキャリアガス導入口112が設置されている。原料容器111および筒状部材113の形状は特に限定されないが、円柱状とすることでキャリアガス131とミスト132が混合した混合気133を円滑に流すことができる。キャリアガス導入口112は筒状部材113の原料容器111内部における下端よりも上方に設けられることが好ましい。このようにすることで、キャリアガス131とミスト132を十分に混合することができる。また原料容器111は、図には示していないが、原料溶液114の消費に応じて補充する機構を備えていても良い。 The raw material container 111 is provided with a carrier gas introduction port 112 for introducing the carrier gas 131. The shapes of the raw material container 111 and the tubular member 113 are not particularly limited, but the cylindrical shape allows the air-fuel mixture 133 in which the carrier gas 131 and the mist 132 are mixed to flow smoothly. The carrier gas introduction port 112 is preferably provided above the lower end of the tubular member 113 inside the raw material container 111. By doing so, the carrier gas 131 and the mist 132 can be sufficiently mixed. Although not shown in the figure, the raw material container 111 may be provided with a mechanism for replenishing the raw material solution 114 according to consumption.

成膜用霧化装置を構成する部材は、原料溶液114に対して化学的に安定かつ十分な機械的強度をもつ材質および構造であれば特に限定されるものではなく、例えば、金属やプラスチック材料、ガラス、金属表面にプラスチック材料をコーティングした材料等が利用できる。 The members constituting the film-forming atomizer are not particularly limited as long as they are materials and structures that are chemically stable with respect to the raw material solution 114 and have sufficient mechanical strength. For example, metal or plastic materials. , Glass, metal surface coated with plastic material, etc. can be used.

超音波発生器120は、少なくとも、超音波発生源121を備えている。また、超音波発生器120は発振器等を備えることで、超音波発生源121を駆動させることができる。また、液槽122は、超音波発生源121から照射された超音波を原料溶液114に伝播するための中間液123を収容するものである。超音波発生源121の超音波の射出面は平坦な形状をしており、照射方向はこの射出面を傾斜させて固定しても良いし、角度調節機構121aにより傾斜させることで変えられるようにしても良い。また、超音波発生源121は、少なくとも1つの超音波振動板を備えていればよく、振動板単体であっても良いし、超音波の照射方向を制御するための手段と組み合わせて構成されていても良い。また、超音波発生源121は、所望のミスト密度や原料容器111のサイズなどに応じて単一または複数設けて良い。超音波発生源121から照射される超音波の周波数は、所望の粒径と粒度のミスト132を発生するものであれば限定されないが、例えば、1.5MHzから4.0MHzを用いると良い。これにより原料溶液114が成膜に適したミクロンサイズの液滴にミスト化される。 The ultrasonic generator 120 includes at least an ultrasonic source 121. Further, the ultrasonic wave generator 120 can drive the ultrasonic wave generation source 121 by including an oscillator or the like. Further, the liquid tank 122 accommodates an intermediate liquid 123 for propagating the ultrasonic waves irradiated from the ultrasonic wave generation source 121 to the raw material solution 114. The ultrasonic wave emitting surface of the ultrasonic wave source 121 has a flat shape, and the irradiation direction may be fixed by inclining this emitting surface, or may be changed by inclining it by the angle adjusting mechanism 121a. You may. Further, the ultrasonic wave generation source 121 may be provided with at least one ultrasonic diaphragm, may be a single diaphragm, or may be configured in combination with means for controlling the irradiation direction of ultrasonic waves. You may. Further, the ultrasonic wave generation source 121 may be provided alone or in plurality depending on the desired mist density, the size of the raw material container 111, and the like. The frequency of the ultrasonic waves emitted from the ultrasonic wave generation source 121 is not limited as long as it generates mist 132 having a desired particle size and particle size, but for example, 1.5 MHz to 4.0 MHz may be used. As a result, the raw material solution 114 is mistized into micron-sized droplets suitable for film formation.

また、超音波発生源121は、液槽122の外側にあり、超音波発生源121の中心が原料容器111の側壁の内側の延長がなす面と筒状部材113の側壁の外側の延長がなす面との間に位置するように設置する。このとき、超音波発生源121の中心を通り、筒状部材113の外壁と平行な直線と、筒状部材113の外壁との距離をdとする。距離dは5mm以上とするのが好ましく、10mm以上とするのがより好ましい。このようにすれば、より高密度のミストをより安定して得ることができるものとなる。 Further, the ultrasonic wave generation source 121 is located on the outside of the liquid tank 122, and the center of the ultrasonic wave generation source 121 is formed by an extension of the inside of the side wall of the raw material container 111 and an extension of the outside of the side wall of the tubular member 113. Install so that it is located between the surface. At this time, let d be the distance between the straight line passing through the center of the ultrasonic wave generation source 121 and parallel to the outer wall of the tubular member 113 and the outer wall of the tubular member 113. The distance d is preferably 5 mm or more, and more preferably 10 mm or more. In this way, a higher density mist can be obtained more stably.

液槽122に収容されている中間液123は、超音波を阻害しなければ特に限定されず、例えば、水やアルコール類およびオイル類などを用いて良い。液槽122等は、中間液123に対して化学的に安定で、ある程度の機械的強度をもつ材質および構造であれば特に限定されるものではない。例えば、金属やプラスチック材料、ガラス、金属表面にプラスチック材料をコーティングした材料等が利用できる。また液槽122は、図には示していないが、中間液123の液量や温度を検知および制御する手段をさらに備えていても良い。 The intermediate liquid 123 contained in the liquid tank 122 is not particularly limited as long as it does not interfere with ultrasonic waves, and for example, water, alcohols, oils, or the like may be used. The liquid tank 122 and the like are not particularly limited as long as they are made of a material and structure that are chemically stable with respect to the intermediate liquid 123 and have a certain degree of mechanical strength. For example, a metal or plastic material, glass, a material obtained by coating a metal surface with a plastic material, or the like can be used. Although not shown in the figure, the liquid tank 122 may further include means for detecting and controlling the liquid amount and temperature of the intermediate liquid 123.

図2は、本発明に係る成膜用霧化装置のミスト発生部を説明する図であり、図1の点線枠箇所Aにおいて、超音波を照射しているときの原料溶液の液面近傍における状態を模式的に示した拡大図である。超音波発生源221の超音波射出面の中心線をuとする。超音波発生源221から原料溶液214の下方より中心線u方向に超音波が照射されると、原料溶液214には超音波照射方向に沿って液柱214pが生じ、同時にミスト化される。 FIG. 2 is a diagram for explaining a mist generating portion of the film forming atomizer according to the present invention, and in the dotted frame portion A of FIG. 1, in the vicinity of the liquid level of the raw material solution when irradiating ultrasonic waves. It is an enlarged view which showed the state schematically. Let u be the center line of the ultrasonic wave emitting surface of the ultrasonic wave generation source 221. When ultrasonic waves are irradiated from below the raw material solution 214 in the center line u direction from the ultrasonic source 221, a liquid column 214p is generated in the raw material solution 214 along the ultrasonic irradiation direction, and at the same time, mist is formed.

このとき、中心線uは筒状部材213の側壁と交わらないように角度調節機構221aにより超音波発生源221を傾ける。また中心線uと筒状部材213の中心を通る線cは任意の点で交わっても良いし、ねじれの位置にあっても良い。また、このとき、超音波発生源221の中心から原料容器211の側壁の延長がなす面までの距離Dは、液柱214pが原料容器211の側壁に著しく遮られない程度とすることが好ましい。これにより混合気の流れが阻害されずに成膜用霧化装置外部へ供給されるようになり、より効率的な成膜が可能となる。また、同時に、未反応生成物やパーティクルの原因となる比較的大きな粒径の液滴が混合気に混入することが抑制されるので、より高品質な膜の形成が可能になる。尚、図1と同じものについては適宜説明を省略する。 At this time, the ultrasonic wave generation source 221 is tilted by the angle adjusting mechanism 221a so that the center line u does not intersect the side wall of the tubular member 213. Further, the center line u and the line c passing through the center of the tubular member 213 may intersect at any point or may be in a twisted position. Further, at this time, it is preferable that the distance D from the center of the ultrasonic wave generation source 221 to the surface formed by the extension of the side wall of the raw material container 211 is such that the liquid column 214p is not significantly blocked by the side wall of the raw material container 211. As a result, the flow of the air-fuel mixture is not obstructed and is supplied to the outside of the atomizing apparatus for film formation, which enables more efficient film formation. At the same time, since droplets having a relatively large particle size, which cause unreacted products and particles, are suppressed from being mixed into the air-fuel mixture, a higher quality film can be formed. The same items as in FIG. 1 will be omitted as appropriate.

なお、本発明における「パーティクル」とは、半導体膜中に取り込まれ膜と一体化したもの及び半導体膜表面に異物として付着したものを含み、膜の表面を観察したときにパーティクルとして観察されるものを指す。また、パーティクルの直径は、光散乱式のパーティクル測定機により測定されたパーティクルのサイズに基づく値である。パーティクルのサイズは、測定機を複数のサイズの標準粒子で校正することで判定される。即ち、測定機でパーティクルを測定した際の測定値と標準粒子を測定した際の測定値を照らし合わせることにより分類される値である。半導体膜の表面におけるパーティクルは、例えばレーザー散乱式のパーティクルカウンタを用いて測定することができる。 The "particles" in the present invention include those that are incorporated into the semiconductor film and integrated with the film and those that adhere to the surface of the semiconductor film as foreign matter, and are observed as particles when the surface of the film is observed. Point to. The particle diameter is a value based on the size of the particles measured by a light scattering type particle measuring machine. Particle size is determined by calibrating the instrument with standard particles of multiple sizes. That is, it is a value classified by comparing the measured value when measuring particles with a measuring machine and the measured value when measuring standard particles. Particles on the surface of the semiconductor film can be measured using, for example, a laser scattering type particle counter.

(成膜装置)
本発明は、さらに図1および図2で説明した成膜用霧化装置を用いた成膜装置を提供する。
(Film formation equipment)
The present invention further provides a film forming apparatus using the film forming atomizing apparatus described with reference to FIGS. 1 and 2.

図3は、本発明に係る成膜装置の構成の一形態を説明する図である。本発明に係る成膜装置300は、少なくとも、原料溶液321を霧化して原料ミスト322を形成する霧化手段320と、ミスト322を基体334に供給して基体334上に膜を形成する成膜手段330とを具備する。成膜装置300は、霧化手段320として、図1および図2で説明した本発明の成膜用霧化装置100を備えている。さらに、キャリアガス供給部311や、霧化手段320と成膜手段330は配管313、324で接続されている。 FIG. 3 is a diagram illustrating one form of the configuration of the film forming apparatus according to the present invention. The film forming apparatus 300 according to the present invention has at least an atomizing means 320 for atomizing the raw material solution 321 to form a raw material mist 322 and a film forming device for supplying the mist 322 to the substrate 334 to form a film on the substrate 334. The means 330 and the like are provided. The film forming apparatus 300 includes the film forming atomizing apparatus 100 of the present invention described with reference to FIGS. 1 and 2 as the atomizing means 320. Further, the carrier gas supply unit 311 and the atomizing means 320 and the film forming means 330 are connected by pipes 313 and 324.

キャリアガス供給部311は、例えば、空気圧縮機や各種ガスボンベまたは窒素ガス分離機などでもよく、また、ガスの供給流量を制御する機構を備えていて良い。 The carrier gas supply unit 311 may be, for example, an air compressor, various gas cylinders, a nitrogen gas separator, or the like, or may include a mechanism for controlling the gas supply flow rate.

配管313、324は原料溶液321や成膜手段330付近における温度などに対して十分な安定性を持つものであれば特に限定されず、石英やポリエチレン、ポリプロピレン、塩化ビニル、シリコン樹脂、ウレタン樹脂、フッ素樹脂などといった一般的な樹脂製の配管を広く用いることができる。 The pipes 313 and 324 are not particularly limited as long as they have sufficient stability with respect to the temperature in the vicinity of the raw material solution 321 and the film forming means 330, and quartz, polyethylene, polypropylene, vinyl chloride, silicon resin, urethane resin, etc. A general resin pipe such as a fluororesin can be widely used.

また、図には示していないが、キャリアガス供給部311から霧化手段320を介さない配管を別途配管324に接続し、混合気352に希釈ガスを供給できるようにしても良い。 Further, although not shown in the figure, a pipe that does not pass through the atomizing means 320 may be separately connected to the pipe 324 from the carrier gas supply unit 311 so that the diluted gas can be supplied to the air-fuel mixture 352.

霧化手段320は、成膜する材料などに応じて複数台を備えていても良い。またこの場合、複数の霧化手段320から成膜手段330へ供給される混合気352は、それぞれ独立して成膜手段330に供給されても良いし、配管324中、あるいは混合用の容器(不図示)などを別途設けて混合しても良い。 A plurality of atomizing means 320 may be provided depending on the material to be formed and the like. Further, in this case, the air-fuel mixture 352 supplied from the plurality of atomizing means 320 to the film forming means 330 may be independently supplied to the film forming means 330, in the pipe 324, or in the mixing container ( (Not shown) or the like may be separately provided and mixed.

成膜手段330は、成膜室331と、成膜室331内に設置され、膜を形成する基体334を保持するサセプター332と、基体334を加熱する加熱手段333を備えていて良い。 The film forming means 330 may include a film forming chamber 331, a susceptor 332 installed in the film forming chamber 331 and holding the substrate 334 for forming the film, and a heating means 333 for heating the substrate 334.

成膜室331の構造等は特に限定されるものではなく、例えば、アルミニウムやステンレスなどの金属を用いて良いし、より高温で成膜を行う場合には石英や炭化シリコンを用いても良い。 The structure of the film forming chamber 331 is not particularly limited, and for example, a metal such as aluminum or stainless steel may be used, or quartz or silicon carbide may be used when the film is formed at a higher temperature.

加熱手段333は基体334、サセプター332および成膜室331の材質や構造によって選定されればよく、例えば、抵抗加熱ヒーターやランプヒーターが好適に用いられる。 The heating means 333 may be selected according to the material and structure of the substrate 334, the susceptor 332, and the film forming chamber 331. For example, a resistance heating heater or a lamp heater is preferably used.

キャリアガス351は、霧化手段320内で形成されたミスト322と混合されて混合気352となり、成膜手段330へと搬送されて成膜が行われる。 The carrier gas 351 is mixed with the mist 322 formed in the atomizing means 320 to form an air-fuel mixture 352, which is conveyed to the film forming means 330 to form a film.

また本発明に係る成膜装置は、さらに排気手段340を備えていて良い。排気手段340は成膜手段330に配管などで接続されていても良いし、間隙を置いて設置されていても良い。また排気手段340は成膜手段330から排出される熱およびガスや生成物に対して安定な素材で構成されてさえいれば、特に構造や構成は限定されず、公知の一般的な排気ファンや排気ポンプが使用できる。また排出されるガスや生成物の性質に応じて、例えば、ミストトラップ、ウェットスクラバー、バグフィルター、除害装置などを備えていても良い。 Further, the film forming apparatus according to the present invention may further include an exhaust means 340. The exhaust means 340 may be connected to the film forming means 330 by a pipe or the like, or may be installed with a gap. Further, the structure and structure of the exhaust means 340 are not particularly limited as long as they are made of a material that is stable against heat, gas and products discharged from the film forming means 330, and a known general exhaust fan or the like. Exhaust pump can be used. Further, depending on the nature of the discharged gas and the product, for example, a mist trap, a wet scrubber, a bag filter, an abatement device and the like may be provided.

図3では、基体334が成膜室331内部に設置される成膜手段330の形態を説明したが、本発明に係る成膜装置ではこれに限らず、図4に示すように成膜手段430として、ミスト422を含む混合気452を吐出するノズル431を用い、サセプター432の上に設置された基体434へ混合気452を直接吹き付けて成膜する成膜装置400としても良い。 In FIG. 3, the form of the film forming means 330 in which the substrate 334 is installed inside the film forming chamber 331 has been described, but the film forming apparatus according to the present invention is not limited to this, and the film forming means 430 is as shown in FIG. A film forming apparatus 400 may be used as a film forming apparatus 400 in which the air-fuel mixture 452 is directly sprayed onto the substrate 434 installed on the susceptor 432 using a nozzle 431 that discharges the air-fuel mixture 452 containing the mist 422.

この場合、ノズル431とサセプター432のうち、いずれかまたは両方が水平方向に駆動する駆動手段を備え、基体434とノズル431の水平方向における相対位置を変化させながら成膜が行われて良い。またサセプター432は基板434を加熱する加熱手段433を備えていて良い。また成膜手段430は、排気手段435を備えていて良い。排気手段435はノズル431と一体化していても良いし、別々に設置されていても良い。尚、図1から3と同じものについては適宜説明を省略する。 In this case, one or both of the nozzle 431 and the susceptor 432 may be provided with a driving means for driving in the horizontal direction, and the film may be formed while changing the relative positions of the substrate 434 and the nozzle 431 in the horizontal direction. Further, the susceptor 432 may be provided with a heating means 433 for heating the substrate 434. Further, the film forming means 430 may include an exhaust means 435. The exhaust means 435 may be integrated with the nozzle 431 or may be installed separately. The same items as those in FIGS. 1 to 3 will be omitted as appropriate.

以下、実施例を挙げて本発明について詳細に説明するが、これは本発明を限定するものではない。 Hereinafter, the present invention will be described in detail with reference to examples, but this does not limit the present invention.

(実施例1)
図1および図2に示した成膜用霧化装置と、図3に示した成膜装置を用いて、α−酸化ガリウムの成膜を行った。
(Example 1)
The film formation of α-gallium oxide was carried out using the film forming atomizer shown in FIGS. 1 and 2 and the film forming apparatus shown in FIG.

成膜用霧化装置にはいずれも硼珪酸ガラス製の原料容器と筒状部材を使用し、また、石英製の成膜室を用意した。キャリアガス供給には窒素ガスが充填されたガスボンベを使用した。ガスボンベと成膜用霧化装置をウレタン樹脂製チューブで接続し、さらに成膜用霧化装置と成膜室を石英製の配管で接続した。 A raw material container made of borosilicate glass and a tubular member were used for the atomizing device for film formation, and a quartz film forming chamber was prepared. A gas cylinder filled with nitrogen gas was used to supply the carrier gas. The gas cylinder and the film-forming atomizer were connected by a urethane resin tube, and the film-forming atomizer and the film-forming chamber were connected by a quartz pipe.

原料溶液として、ガリウムアセチルアセトナート0.02mol/Lの水溶液に濃度34%の塩酸を体積比で1%加え、スターラーで60分間攪拌したものを用意し、これを原料容器に充填した。成膜用霧化装置は2基の超音波振動板(周波数2.4MHz、照射角度80°)を備えたものを使用した。超音波振動板の中心を筒状部材の側壁から外側に10mm離れた位置とし、図2のように、中心線uが筒状部材の側壁と交わらないように超音波振動板を設置した。 As a raw material solution, 1% by volume of hydrochloric acid having a concentration of 34% was added to an aqueous solution of gallium acetylacetonate 0.02 mol / L, and the mixture was stirred with a stirrer for 60 minutes, and this was filled in a raw material container. As the atomizing apparatus for film formation, an apparatus equipped with two ultrasonic diaphragms (frequency 2.4 MHz, irradiation angle 80 °) was used. The center of the ultrasonic diaphragm was set at a position 10 mm outward from the side wall of the tubular member, and the ultrasonic diaphragm was installed so that the center line u did not intersect the side wall of the tubular member as shown in FIG.

次に、厚さ0.6mm、直径4インチ(約10cm)のc面サファイア基板を、成膜室内に設置した石英製のサセプターに載置し、基板温度が500℃になるように加熱した。 Next, a c-plane sapphire substrate having a thickness of 0.6 mm and a diameter of 4 inches (about 10 cm) was placed on a quartz susceptor installed in the film formation chamber and heated so that the substrate temperature became 500 ° C.

次に、超音波振動板により水を通じて原料容器内の前駆体に超音波振動を伝播させて、原料溶液を霧化(ミスト化)した。 Next, the ultrasonic vibration was propagated to the precursor in the raw material container through water by the ultrasonic diaphragm to atomize (mist) the raw material solution.

次に、原料容器に窒素ガスを5L/minの流量で加え、成膜室にミストと窒素ガスの混合気を60分間供給して成膜を行った。この直後、窒素ガスの供給を停止し、成膜室への混合気供給を停止した。 Next, nitrogen gas was added to the raw material container at a flow rate of 5 L / min, and a mixture of mist and nitrogen gas was supplied to the film forming chamber for 60 minutes to perform film formation. Immediately after this, the supply of nitrogen gas was stopped, and the supply of the air-fuel mixture to the film forming chamber was stopped.

作製した積層体の結晶層は、X線回折測定で2θ=40.3°にピークが現れたことから、α相のGaであることが確認された。 The crystal layer of the produced laminate showed a peak at 2θ = 40.3 ° by X-ray diffraction measurement, confirming that it was an α-phase Ga 2 O 3.

この後、作製した膜の膜厚を光反射率解析で測定し、成長速度を算出した。また、膜上のパーティクル(直径0.5μm以上)密度を基板検査機(KLA candela−CS10)で評価した。 After that, the film thickness of the produced film was measured by light reflectance analysis, and the growth rate was calculated. Further, the density of particles (diameter 0.5 μm or more) on the film was evaluated by a substrate inspection machine (KLA candela-CS10).

(実施例2)
窒素ガス流量を10L/minとした以外は実施例1と同様に成膜を行った。
(Example 2)
The film was formed in the same manner as in Example 1 except that the nitrogen gas flow rate was set to 10 L / min.

作製した積層体の結晶層は、X線回折測定で2θ=40.3°にピークが現れたことから、α相のGaであることが確認された。 The crystal layer of the produced laminate showed a peak at 2θ = 40.3 ° by X-ray diffraction measurement, confirming that it was an α-phase Ga 2 O 3.

この後、実施例1と同様に膜を評価した。 After that, the film was evaluated in the same manner as in Example 1.

(実施例3)
成膜装置に図4で示した成膜装置を用いた他は、実施例1と同様の装置および原料溶液を使用してα−酸化ガリウムの成膜を行った。ミスト吐出ノズルには石英製のものを使用した。サセプターにはアルミ製ホットプレートを使用し、基板を450℃に加熱した。次にサセプターを10mm/sの速度でミスト吐出ノズルの下を水平方向に往復駆動させ、さらにミスト吐出ノズルからサセプター上の基板へ混合気を5L/min供給して60分間成膜を行った。
(Example 3)
Α-Gallium oxide was deposited using the same apparatus and raw material solution as in Example 1 except that the film forming apparatus shown in FIG. 4 was used as the film forming apparatus. A quartz mist discharge nozzle was used. An aluminum hot plate was used as the susceptor, and the substrate was heated to 450 ° C. Next, the susceptor was reciprocated in the horizontal direction under the mist discharge nozzle at a speed of 10 mm / s, and 5 L / min of air-fuel mixture was supplied from the mist discharge nozzle to the substrate on the susceptor to form a film for 60 minutes.

作製した積層体の結晶層は、X線回折測定で2θ=40.3°にピークが現れたことから、α相のGaであることが確認された。この後、実施例1と同様に膜を評価した。 The crystal layer of the produced laminate showed a peak at 2θ = 40.3 ° by X-ray diffraction measurement, confirming that it was an α-phase Ga 2 O 3. After that, the film was evaluated in the same manner as in Example 1.

(比較例1)
超音波を、筒状部材の側壁に向けて照射した他は、実施例1と同様に成膜を行った。
(Comparative Example 1)
A film was formed in the same manner as in Example 1 except that the ultrasonic waves were irradiated toward the side wall of the tubular member.

作製した積層体の結晶層は、X線回折測定で2θ=40.3°にピークが現れたことから、α相のGaであることが確認された。この後、実施例1と同様に膜を評価した。 The crystal layer of the produced laminate showed a peak at 2θ = 40.3 ° by X-ray diffraction measurement, confirming that it was an α-phase Ga 2 O 3. After that, the film was evaluated in the same manner as in Example 1.

(比較例2)
超音波を、筒状部材の側壁に向けて照射した他は、実施例2と同様に成膜を行った。
(Comparative Example 2)
A film was formed in the same manner as in Example 2 except that the ultrasonic wave was irradiated toward the side wall of the tubular member.

作製した積層体の結晶層は、X線回折測定で2θ=40.3°にピークが現れたことから、α相のGaであることが確認された。この後、実施例1と同様に膜を評価した。 The crystal layer of the produced laminate showed a peak at 2θ = 40.3 ° by X-ray diffraction measurement, confirming that it was an α-phase Ga 2 O 3. After that, the film was evaluated in the same manner as in Example 1.

実施例1、2、3及び比較例1、2における成長速度および得られた膜のパーティクル密度を表1に示す。 Table 1 shows the growth rate and the particle density of the obtained film in Examples 1, 2 and 3 and Comparative Examples 1 and 2.

Figure 2021133363
Figure 2021133363

表1より、実施例1、2、3に示されるように、本発明に係る成膜装置は、高い成長速度で、かつパーティクルが少ない高品質な膜を作製することのできる優れたものであることが分かる。一方、従来技術の成膜用霧化装置を用いた比較例1、2では、成長速度が低く、また多くのパーティクルが付着していた。 As shown in Examples 1, 2 and 3 from Table 1, the film forming apparatus according to the present invention is an excellent one capable of producing a high-quality film having a high growth rate and few particles. You can see that. On the other hand, in Comparative Examples 1 and 2 using the conventional atomizing apparatus for film formation, the growth rate was low and many particles were attached.

(実施例4)
成膜時間、すなわち、成膜室にミストと窒素ガスの混合気を供給する時間を120分間としたこと以外は実施例1と同じ条件で成膜を行い、膜厚1μm以上の半導体膜の成膜を行った。そして、成膜して得た膜の表面のパーティクル(直径0.3μm以上)密度を、基板検査機(KLA candela−CS10)で評価した。
(Example 4)
The film was formed under the same conditions as in Example 1 except that the film forming time, that is, the time for supplying the mixture of mist and nitrogen gas to the film forming chamber was 120 minutes, to form a semiconductor film having a film thickness of 1 μm or more. The membrane was made. Then, the density of particles (diameter 0.3 μm or more) on the surface of the film obtained by film formation was evaluated by a substrate inspection machine (KLA candela-CS10).

(実施例5)
成膜時間を120分間としたこと以外は実施例2と同条件で成膜し、実施例4と同条件で評価を行った。
(Example 5)
The film was formed under the same conditions as in Example 2 except that the film formation time was 120 minutes, and the evaluation was performed under the same conditions as in Example 4.

(実施例6)
成膜時間を120分間としたこと以外は実施例3と同条件で成膜し、実施例4と同条件で評価を行った。
(Example 6)
The film was formed under the same conditions as in Example 3 except that the film formation time was 120 minutes, and the evaluation was performed under the same conditions as in Example 4.

(比較例3)
成膜時間を120分間としたこと以外は比較例1と同条件で成膜し、実施例4と同条件で評価を行った。
(Comparative Example 3)
The film was formed under the same conditions as in Comparative Example 1 except that the film formation time was 120 minutes, and the evaluation was performed under the same conditions as in Example 4.

(比較例4)
成膜時間を120分間としたこと以外は比較例2と同条件で成膜し、実施例4と同条件で評価を行った。
(Comparative Example 4)
The film was formed under the same conditions as in Comparative Example 2 except that the film formation time was 120 minutes, and the evaluation was performed under the same conditions as in Example 4.

実施例4、5、6及び比較例3、4における成長速度および得られた膜のパーティクル密度を表2に示す。 Table 2 shows the growth rates and the particle densities of the obtained films in Examples 4, 5 and 6 and Comparative Examples 3 and 4.

Figure 2021133363
Figure 2021133363

表2より、実施例4、5、6に示されるように、本発明に係る成膜装置を用いて成膜を行った場合、高い成長速度で、かつパーティクルが少ない高品質な膜を作製することができることが分かる。特に、直径0.3μm以上のパーティクル密度が50個/cm以下である半導体膜を得ることができた。一方、従来技術の成膜用霧化装置を用いた比較例3、4では、成長速度が低く、また多くのパーティクルが付着していた。 From Table 2, as shown in Examples 4, 5 and 6, when film formation is performed using the film forming apparatus according to the present invention, a high-quality film having a high growth rate and few particles is produced. You can see that you can. In particular, it was possible to obtain a semiconductor film having a particle density of 50 particles / cm 2 or less having a diameter of 0.3 μm or more. On the other hand, in Comparative Examples 3 and 4 using the conventional atomizing apparatus for film formation, the growth rate was low and many particles were attached.

なお、本発明は、上記実施形態に限定されるものではない。上記実施形態は例示であり、本発明の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本発明の技術的範囲に包含される。 The present invention is not limited to the above embodiment. The above-described embodiment is an example, and any object having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same effect and effect is the present invention. Is included in the technical scope of.

100…成膜用霧化装置、 111…原料容器、 112…キャリアガス導入口、
113…筒状部材、 114…原料溶液、 120…超音波発生器、
121…超音波発生源、 121a…角度調節機構、 122…液槽、
123…中間液、 131…キャリアガス、 132…ミスト、 133…混合気、
211…原料容器、 213…筒状部材、 214…原料溶液、 214p…液柱、
221…超音波発生源、 221a…角度調節機構、
300…成膜装置、 311…キャリアガス供給部、 313、324…配管、
320…霧化手段(成膜用霧化装置)、 321…原料溶液、 322…ミスト、
330…成膜手段、 331…成膜室、 332…サセプター、 333…加熱手段、
334…基体、 340…排気手段、 351…キャリアガス、 352…混合気、
400…成膜装置、 422…ミスト、 430…成膜手段、 431…ノズル、
432…サセプター、 433…加熱手段、 434…基体、 435…排気手段、
452…混合気。
100 ... Atomizer for film formation, 111 ... Raw material container, 112 ... Carrier gas inlet,
113 ... Cylindrical member, 114 ... Raw material solution, 120 ... Ultrasonic generator,
121 ... Ultrasonic source, 121a ... Angle adjustment mechanism, 122 ... Liquid tank,
123 ... Intermediate liquid, 131 ... Carrier gas, 132 ... Mist, 133 ... Air-fuel mixture,
211 ... Raw material container, 213 ... Cylindrical member, 214 ... Raw material solution, 214p ... Liquid column,
221 ... Ultrasonic source, 221a ... Angle adjustment mechanism,
300 ... film forming apparatus, 311 ... carrier gas supply unit, 313, 324 ... piping,
320 ... Atomizing means (atomizing device for film formation), 321 ... Raw material solution, 322 ... Mist,
330 ... film formation means, 331 ... film formation chamber, 332 ... susceptor, 333 ... heating means,
334 ... Base, 340 ... Exhaust means, 351 ... Carrier gas, 352 ... Air-fuel mixture,
400 ... film forming apparatus, 422 ... mist, 430 ... film forming means, 431 ... nozzle,
432 ... susceptor, 433 ... heating means, 434 ... base, 435 ... exhaust means,
452 ... Air-fuel mixture.

Claims (3)

原料溶液を収容する原料容器と、前記原料容器の内部と外部を空間的に接続し、且つその下端が前記原料容器内において前記原料溶液の液面に触れないように設置された筒状部材と、超音波を照射する超音波発生源を一つ以上有する超音波発生器と、前記超音波を前記原料溶液に中間液を介して伝播させる液槽とを有する成膜用霧化装置であって、
前記超音波発生源は、前記液槽の外側にあり、
前記超音波発生源の中心が前記原料容器の側壁の内側の延長がなす面と前記筒状部材の側壁の外側の延長がなす面との間にあり、
前記超音波発生源の超音波射出面の中心線をuとしたとき、前記中心線uが前記筒状部材の側壁と交わらないように超音波発生源が設けられていることを特徴とする成膜用霧化装置。
A raw material container for accommodating a raw material solution, and a tubular member installed so as to spatially connect the inside and the outside of the raw material container and prevent the lower end of the raw material container from touching the liquid surface of the raw material solution in the raw material container. An atomizing device for film formation having an ultrasonic generator having one or more ultrasonic generation sources for irradiating ultrasonic waves, and a liquid tank for propagating the ultrasonic waves to the raw material solution via an intermediate liquid. ,
The ultrasonic source is located outside the liquid tank and is located outside the liquid tank.
The center of the ultrasonic wave generation source is between the surface formed by the inner extension of the side wall of the raw material container and the surface formed by the outer extension of the side wall of the tubular member.
When the center line of the ultrasonic emission surface of the ultrasonic wave generation source is u, the ultrasonic wave generation source is provided so that the center line u does not intersect with the side wall of the tubular member. Atomizer for membranes.
前記超音波発生源の中心を通り、前記筒状部材の外壁と平行な直線と前記筒状部材の外壁との距離dが、5mm以上となるように超音波発生源が設けられていることを特徴とする請求項1に記載の成膜用霧化装置。 The ultrasonic wave generation source is provided so that the distance d between the straight line passing through the center of the ultrasonic wave generation source and parallel to the outer wall of the tubular member and the outer wall of the tubular member is 5 mm or more. The atomizing apparatus for film formation according to claim 1. 原料溶液を霧化して原料ミストを形成する霧化手段と、前記ミストを基体に供給して前記基体上に膜を形成する成膜手段とを少なくとも具備する成膜装置であって、
前記霧化手段が請求項1又は請求項2に記載の霧化装置であることを特徴とする成膜装置。
A film forming apparatus comprising at least an atomizing means for atomizing a raw material solution to form a raw material mist and a film forming means for supplying the mist to a substrate to form a film on the substrate.
A film forming apparatus according to claim 1 or 2, wherein the atomizing means is the atomizing apparatus.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10140356A (en) * 1996-11-12 1998-05-26 Matsushita Electric Ind Co Ltd Vaporizing device and cvd device
JP2005305233A (en) * 2004-04-19 2005-11-04 Shizuo Fujita Atomization apparatus for forming film
WO2015019468A1 (en) * 2013-08-08 2015-02-12 東芝三菱電機産業システム株式会社 Atomizer
JP2016187764A (en) * 2015-03-30 2016-11-04 本多電子株式会社 Ultrasonic atomization device
JP2018070422A (en) * 2016-11-01 2018-05-10 国立大学法人 和歌山大学 Production method of gallium oxide, and crystal growth apparatus
JP2018142637A (en) * 2017-02-28 2018-09-13 株式会社Flosfia Processing method
JP2020188170A (en) * 2019-05-15 2020-11-19 トヨタ自動車株式会社 Mist generation device and deposition device
JP2020196930A (en) * 2019-06-03 2020-12-10 トヨタ自動車株式会社 Mist generator, film deposition apparatus, and film deposition method using the film deposition apparatus

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4990707B2 (en) * 2007-07-24 2012-08-01 パナソニック株式会社 Ultrasonic fog generator
JP5470514B2 (en) * 2009-12-22 2014-04-16 ナノミストテクノロジーズ株式会社 Ultrasonic atomization method and atomizer
JP5793732B2 (en) 2011-07-27 2015-10-14 高知県公立大学法人 Highly crystalline conductive α-type gallium oxide thin film doped with dopant and method for producing the same
JP6137668B2 (en) 2012-08-26 2017-05-31 国立大学法人 熊本大学 Zinc oxide crystal layer manufacturing method and mist chemical vapor deposition apparatus
CN108472676B (en) * 2015-12-11 2021-04-09 东芝三菱电机产业系统株式会社 Droplet coating and film forming apparatus and droplet coating and film forming method
KR102354893B1 (en) * 2017-05-31 2022-01-25 도시바 미쓰비시덴키 산교시스템 가부시키가이샤 The application head of the mist application|coating film-forming apparatus, and its maintenance method

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10140356A (en) * 1996-11-12 1998-05-26 Matsushita Electric Ind Co Ltd Vaporizing device and cvd device
JP2005305233A (en) * 2004-04-19 2005-11-04 Shizuo Fujita Atomization apparatus for forming film
WO2015019468A1 (en) * 2013-08-08 2015-02-12 東芝三菱電機産業システム株式会社 Atomizer
JP2016187764A (en) * 2015-03-30 2016-11-04 本多電子株式会社 Ultrasonic atomization device
JP2018070422A (en) * 2016-11-01 2018-05-10 国立大学法人 和歌山大学 Production method of gallium oxide, and crystal growth apparatus
JP2018142637A (en) * 2017-02-28 2018-09-13 株式会社Flosfia Processing method
JP2020188170A (en) * 2019-05-15 2020-11-19 トヨタ自動車株式会社 Mist generation device and deposition device
JP2020196930A (en) * 2019-06-03 2020-12-10 トヨタ自動車株式会社 Mist generator, film deposition apparatus, and film deposition method using the film deposition apparatus

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